This invention relates to the use of formulations containing at least one fluorinated component for reducing the friction between conveyors and the articles transported thereon.
In the food industry and especially in beverage factories, the containers to be filled in the bottling plants are conveyed by conveyors differing in design and constituent materials, for example by platform conveyors or chain-like arrangements which are generally referred to hereinafter as chain conveyors. The conveyors establish the connection between the various optional treatment stages of the bottling process such as, for example, the unpacker, bottle washer, filler, closer, labeller, packer, etc. The containers may assume various forms, more particularly glass and plastic bottles, cans, glasses, casks, beverage containers (kegs), paper and paperboard containers. To guarantee uninterrupted operation, the conveyor chains have to be suitably lubricated to avoid excessive friction with the containers. Dilute aqueous solutions containing suitable friction-reducing ingredients are normally used for lubrication. The chain conveyors are contacted with the aqueous solutions by dipping or spraying, for example, the corresponding lubrication systems being known as dip lubrication or automatic belt lubrication or central chain lubrication systems.
The chain lubricants hitherto used as lubricants are mostly based on fatty acids in the form of their water-soluble alkali metal or alkanolamine salts or on fatty amines, preferably in the form of their organic or inorganic salts.
Whereas both classes of substances can be used without difficulty in dip lubrication, they are attended by a number of disadvantages in the central chain lubrication systems typically in use today. Thus, DE-A-23 13 330 describes soap-based lubricants containing aqueous mixtures of C16-18 fatty acid salts and surface-active substances. Soap-based lubricants such as these have the following disadvantages:
1. They react with the hardness ions in water, i.e. the alkaline earth metal ions, and other ingredients of water to form poorly soluble metal soaps, so-called primary alkaline earth metal soaps.
2. A reaction takes place between the soap-based lubricants and carbon dioxide dissolved in water or in the product to be bottled.
3. The in-use solution thus prepared is always germ-promoting.
4. Where hard water is used, ion exchangers have to be employed to soften the water which means an additional source of germs (and is therefore hardly encountered in practice) or, alternatively, products of high complexing agent content have to be used which is ecologically unsafe.
5. Increased foaming occurs which can cause problems in particular at the bottle inspector (automatic bottle control) and results in greater wetting of the transport containers.
6. Most of these products contain solvents.
7. The cleaning effect of the products is poor so that separate cleaning is necessary.
8. Corresponding soap-based lubricant preparations show pH-dependent performance.
9. In addition, soap-based lubricant preparations are dependent on the water temperature.
10. Soap-based lubricants show poor stability in storage, particularly at low temperatures.
11. The EDTA (ethylenediamine tetraacetate) present in many products is known to have poor biodegradability.
12. Soap-based lubricant preparations are not suitable for all plastic transport containers because, in many cases, they give rise to stress cracking in the transport container.
Besides soap-based lubricants, lubricants based on fatty amines are mainly used. Thus, DE-A-36 31 953 describes a process for lubricating chain-type bottle conveyors in bottling factories, more particularly in breweries, and for cleaning the conveyors with a liquid cleaning composition, characterized in that the chain-type bottle conveyors are lubricated with belt lubricants based on neutralized primary fatty amines which preferably contain 12 to 18 carbon atoms and which have an unsaturated component of more than 10%.
EP-A-0 372 628 discloses fatty amine derivatives corresponding to the following formulae: 
in which
R1 is a saturated or unsaturated, branched or linear alkyl group containing 8 to 22 carbon atoms,
R2 is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms or xe2x80x94Axe2x80x94NH2,
A is a linear or branched alkylene group containing 1 to 8 carbon atoms and
A1 is a linear or branched alkylene group containing 2 to 4 carbon atoms, as lubricants.
In addition, lubricants based on N-alkylated fatty amine derivatives which contain at least one secondary and/or tertiary amine are known from DE-A-39 05 548.
DE-A42 06 506 relates to soapless lubricants based on amphoteric compounds, primary, secondary and/or tertiary amines and/or salts of such amines corresponding to general formulae (I), (IIa), (IIb), (IIIa), (IIIb), (IIIc), (IVa) and (IVb): xe2x80x83R4xe2x80x94NHxe2x80x94R5xe2x80x83xe2x80x83(IIa)
R4xe2x80x94N+H2xe2x80x94R5Xxe2x88x92xe2x80x83xe2x80x83(IIb)
R4xe2x80x94NHxe2x80x94(CH2)3NH2xe2x80x83xe2x80x83(IIIa)
R4xe2x80x94NHxe2x80x94(CH2)3N+H3Xxe2x88x92xe2x80x83xe2x80x83(IIIb)
R4xe2x80x94N+H2xe2x80x94(CH2)3-N+H32Xxe2x88x92xe2x80x83xe2x80x83(IIIc)
R4xe2x80x94NR7R8xe2x80x83xe2x80x83(IVa) and/or
R4xe2x80x94N+HR7R8Xxe2x88x92xe2x80x83xe2x80x83(IVb)
in which
R is a saturated or mono- or polyunsaturated, linear or branched alkyl group containing 6 to 22 carbon atoms which may optionally be substituted by xe2x80x94OH, xe2x80x94NH2, xe2x80x94NHxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94(CH2CH2O)lxe2x80x94 or xe2x80x94(CH2CH2CH2O)lxe2x80x94,
R1 is hydrogen, an alkyl group containing 1 to 4 carbon atoms, a hydroxyalkyl group containing 1 to 4 carbon atoms or a group xe2x80x94R3COOM,
R2 is hydrogen, an alkyl group containing 1 to 4 carbon atoms or a hydroxyalkyl group containing 1 to 4 carbon atoms, but only where M represents a negative charge,
R3 is a saturated or mono- or polyunsaturated, linear or branched alkyl group containing 1 to 12 carbon atoms which may optionally be substituted by xe2x80x94OH, xe2x80x94NH2, xe2x80x94NHxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94(CH2CH2O)lxe2x80x94 or xe2x80x94(CH2CH2CH2O)lxe2x80x94,
R4 is a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl group containing 6 to 22 carbon atoms which may contain at least one amine, imine, hydroxy, halogen and/or carboxy group as substituent, a substituted or unsubstituted phenyl group which may contain at least one amine, imine, hydroxy,3 halogen, carboxy and/or a linear or branched, saturated or mono- or polyunsaturated alkyl group containing 6 to 22 carbon atoms as substituent,
R5 is hydrogen orxe2x80x94independently of R4xe2x80x94has the same meaning as R4,
Xxe2x88x92 is an anion from the group consisting of amidosulfonate, nitrate, halide, sulfate, hydrogen carbonate, carbonate, phosphate or R6xe2x80x94COOxe2x80x94 where
R6 is hydrogen, a substituted or unsubstituted, linear or branched alkyl group containing 1 to 20 carbon atoms or alkenyl group containing 2 to 20 carbon atoms, which may contain at least one hydroxy, amine or imine group as substituent, or a substituted or unsubstituted phenyl group which may contain an alkyl group with 1 to 20 carbon atoms as substituent, and
R7 and R8 independently of one another represent a substituted or unsubstituted, linear or branched alkyl group containing 1 to 20 carbon atoms or alkenyl group containing 2 to 20 carbon atoms which may contain at least one hydroxy, amine or imine group as substituent, or a substituted or unsubstituted phenyl group which may contain an alkyl group with 1 to 20 carbon atoms as substituent,
M is hydrogen, alkali metal, ammonium, an alkyl group containing 1 to 4 carbon atoms, a benzyl group or a negative charge,
n is an integer of 1 to 12,
m is an integer of 0 to 5 and
l is a number of 0 to 5,
containing alkyl dimethylamine oxides and/or alkyl oligoglycosides as nonionic surfactants.
EP-B-629 234 discloses a lubricant combination consisting of
a) one or more compounds corresponding to the following formula: 
xe2x80x83in which
R1 is a saturated or mono- or polyunsaturated, linear or branched alkyl group containing 6 to 22 carbon atoms which may optionally be substituted by xe2x80x94OH, xe2x80x94NH2xe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94COxe2x80x94, halogen or a carboxyl group,
R2 is a carboxyl group containing 2 to 7 carbon atoms,
M is hydrogen, alkali metal, ammonium, an alkyl group containing 1 to 4 carbon atoms or a benzyl group and
n is an integer of 1 to 6,
b) at least one organic carboxylic acid selected from monobasic or polybasic, saturated or mono- or polyunsaturated carboxylic acids containing 2 to 22 carbon atoms,
c) optionally water and additives and/or auxiliaries.
WO 94/03562 describes a lubricant concentrate based on fatty amines and optionally typical diluents or auxiliaries and additives, characterized in that it contains at least one polyamine derivative of a fatty amine and/or a salt of such an amine, the percentage content of the polyamine derivatives of fatty amines in the formulation as a whole being from 1 to 100% by weight.
In one preferred embodiment of WO 94/03562, this lubricant concentrate contains at least one polyamine derivative of a fatty amine corresponding to the following general formula:
Rxe2x80x94Axe2x80x94(CH2)kxe2x80x94NHxe2x80x94[(CH2)lxe2x80x94NH]yxe2x80x94(CH2)mxe2x80x94NH2.(H+Xxe2x88x92)n
in which
R is a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl group containing 6 to 22 carbon atoms, the substituents being selected from amino, imino, hydroxy, halogen and carboxy, or a substituted or unsubstituted phenyl group, the substituents being selected from amino, imino, hydroxy, halogen, carboxy and a linear or branched, saturated or mono- or polyunsaturated alkyl group containing 6 to 22 carbon atoms,
A represents either xe2x80x94NHxe2x80x94 or xe2x80x94Oxe2x80x94,
Xxe2x88x92 is an anion of an inorganic or organic acid,
k, l and m independently of one another are integers of 1 to 6,
y is 0, 1, 2 or 3 where A=xe2x80x94NHxe2x80x94 or 1, 2, 3 or 4 where A=xe2x80x94Oxe2x80x94 and
n is an integer of 0 to 6.
Lubricants based on polytetrafluoroethylene are used in some bottling plants. They are present in the form of dispersions and are not applied to the chains in the usual way through nozzles, but instead by brushes. These lubricants have the advantage that they significantly reduce the friction between the conveyor belts and the containers transported thereon. In addition, the polytetrafluoroethylene adheres very strongly to the chains. A disadvantage encountered in practice was that the overall hygienic state in regard to germ population and soiling of the chain conveyors was adversely affected to such an extent that the performance profile of the lubricant gradually deteriorated as a result of the increase in soiling.
Another disadvantage encountered was that the dispersions of polytetrafluoroethylene were not stable in storage and gradually separated. The result of this is that, over a prolonged period, varying amounts of active substance are applied to the chain conveyors.
When an attempt was made to clean the chain conveyors, it was found that the layer of lubricant was very difficult to remove from the chains.
In addition, investigation of the compatibility of polytetrafluoroethylene dispersions with plastics showed that they produce stress cracks in PET bottles.
The problem addressed by the present invention was to provide lubricants based on organic fluorine compounds which, on the one hand, would be stable in storage and, on the other hand, compatible with plastic containers and which at the same time would improve lubricating performance by comparison with the amines typically used as lubricants.
The present invention relates to the use of formulations containing at least one fluorinated component selected from the groups of
a) perfluorinated or partly fluorinated monomeric organic compounds,
b) pure and mixed dimers and oligomers based on at least one perfluorinated or partly fluorinated organic monomer,
c) pure and mixed polymers based on at least one perfluorinated or partly fluorinated organic monomer, the polymer containing at least one monomer unit which contains either less than 70% by weight of fluorine, based on the weight of the total monomer unit, or more than 2 carbon atoms,
for reducing the friction between conveyor installations and the containers transported thereon.
According to the invention, the definition of the boundary between oligomers and polymers is based on the generally known characterization of polymers which are made up of so many identical or similar low molecular weight units (monomers) that the physical properties of these substances, particularly their viscoelasticity, do not change significantly when the number of units is increased or reduced by one unit. This is generally the case when the average molecular weight of the xe2x80x9cpolymersxe2x80x9d is 10,000 g/mole or more.
The term oligomers is used for the low molecular weight dimers, trimers and other lower members of the polymer-homolog series.
In one preferred embodiment, group a) comprises at least perfluorinated and partly fluorinated surfactants, alkanes, ethers and amines, the formulations used in accordance with the invention in one particularly preferred embodiment containing ammonium perfluoroalkyl sulfonates, lithium perfluoroalkyl sulfonates, potassium perfluoroalkyl sulfonates, amine perfluoroalkyl sulfonates, sodium perfluoroalkyl sulfonates, potassium fluoroalkyl carboxylates, quaternary fluorinated alkyl ammonium iodides, ammonium perfluoroalkyl carboxylates, fluorinated alkyl polyoxyethylene ethanols, fluorinated alkyl alkoxylates, fluorinated alkyl esters in concentrations of 0.001 to 10%. The fluorinated components of group c) are preferably perfluorinated and/or partly fluorinated alkoxy polymers which, in one particularly preferred embodiment, are obtainable from the copolymerization of tetrafluoroethylene and perfluoroalkoxyvinyl ethers.
In another preferred embodiment, the formulations to be used in accordance with the invention contain at least perfluorinated and/or partly fluorinated polyethers from group c).
In another preferred embodiment, the formulations to be used in accordance with the invention are present in the form of solutions, gels, emulsions, pastes, dispersions.
In one preferred embodiment, the formulations to be used in accordance with the invention additionally contain at least one antimicrobial component selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenyl alkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butyl carbamate, iodine, iodophors, peroxides, the formulations to be used in accordance with the invention in one particularly preferred embodiment containing one or more compounds selected from ethanol, n-propanol, i-propanol, butane-1,3-diol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, 2-benzyl4-chlorophenol, 2,2xe2x80x2-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)-urea, N,Nxe2x80x2-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octaneamine)-dihydrochloride, N,Nxe2x80x2-bis-(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecane diimidoamide, quaternary ammonium compounds or alkyl amines, guanidines, amphoteric surfactants as antimicrobial components.
Whereas stable formulations of polytetrafluoroethylene dispersions and antimicrobial components are very difficult or impossible to obtain, the formulations containing antimicrobial components to be used in accordance with the invention generally give stable formulations.
In another preferred embodiment, the formulations to be used in accordance with the invention additionally contain at least one component selected from the group of polyhydroxy compounds, more particularly from the groups of polyalcohols and carbohydrates, andxe2x80x94in one most particularly preferred embodimentxe2x80x94a component selected from polyhydric alcohols, preferably alkanediols, alkanetriols, more particularly glycerol, and the polyethers derived therefrom and glucose, arabinose, ribulose, fructose and the oligo- and/or polysaccharides derived therefrom and their esters and ethers.
In another preferred embodiment, the formulations to be used in accordance with the invention contain other components selected from the groups of surfactants and solubilizing agents, at least one alkyl polyglycoside being present as surfactant in a particularly preferred embodiment. Other preferred constituents are fatty alkylamines and/or alkoxylates thereof, more particularly cocofatty amine ethoxylates, and/or imidazoline compounds and/or amphoteric surfactants and/or nonionic surfactants and/or ether carboxylic acids and/or ether amine compounds. In another preferred embodiment, paraffin compounds are added to the formulations to be used in accordance with the invention. The water content of the formulations to be used in accordance with the invention is preferably below 20% by weight and more preferably below 10% by weight, based on the formulation as a whole, the formulations in particularly special embodiments containing no water which, in the context of the invention, means that water is not intentionally added to the formulation. In practice, the formulations to be used in accordance with the invention are applied to the chain conveyors. In the most favorable case, the transport of the containers on the conveyors is not accompanied by foaming. By comparison with conventional lubricants which are diluted with water by a factor of more than 100 in automatic conveyor installations, the formulations to be used in accordance with the invention reduce frictional resistance between the conveyor and the containers transported thereon by more than 20% by for the same quantities by weight of active lubricating components applied to the conveyor installation over a certain period of time. This is demonstrated by the following Examples.